Phase-pure lithium aluminium titanium phosphate and method for its production and its use

ABSTRACT

The present invention relates to a method for producing lithium aluminum titanium phosphates of the general formula Li 1+x Ti 2−x Al x (PO 4 ) 3,  wherein x is ≦0.4, a method for their production as well as their use as solid-state electrolytes in lithium ion accumulators.

The present invention relates to phase-pure lithium aluminum titaniumphosphate, a method for its production, its use, as well as a secondarylithium ion battery containing the phase-pure lithium aluminum titaniumphosphate.

Recently, battery-powered motor vehicles have increasingly become thefocal point of research and development because of the increasing lackof fossil raw materials in the near future.

In particular lithium ion accumulators (also called secondary lithiumion batteries) proved to be the most promising battery models for suchapplications.

These so-called “lithium ion batteries” are also widely used in fieldssuch as power tools, computers, mobile telephones etc. In particular thecathodes and electrolytes, but also the anodes, consist oflithium-containing materials.

LiMn₂O₄ and LiCoO₂ for example have been used for some time as cathodematerials. Recently, in particular since the work of Goodenough et al.(U.S. Pat. No. 5,910,382), also doped or non-doped mixed lithiumtransition metal phosphates, in particular LiFePO₄.

Normally, for example graphite or also, as already mentioned above,lithium compounds such as lithium titanates are used as anode materialsin particular for large-capacity batteries.

By lithium titanates are meant here the doped or non-doped lithiumtitanium spinels of the Li_(1+x)Ti_(2−x)O₄ type with 0≦x≦⅓ of the spacegroup Fd3m and all mixed titanium oxides of the generic formulaLi_(x)Ti_(y)O(0≦x, y≦1).

Normally, lithium salts or their solutions are used for the electrolytein such lithium ion accumulators.

Ceramic separators such as Separion® commercially available in themeantime for example from Evonik Degussa (DE 196 53 484 A1) have alsobeen proposed. However, Separion contains, not a solid-stateelectrolyte, but ceramic fillers such as nanoscale Al₂O₃ and SiO₂.

Lithium titanium phosphates have for some time been mentioned as solidelectrolytes (JP A 1990 2-225310). Lithium titanium phosphates have,depending on the structure and doping, an increased lithium ionconductivity and a low electrical conductivity, which, also in additionto their hardness, makes them very suitable as solid electrolytes insecondary lithium ion batteries.

Aono et al. have described the ionic (lithium) conductivity of doped andnon-doped lithium titanium phosphates (J. Electrochem. Soc., Vol. 137,No. 4, 1990, pp. 1023-1027, J. Electrochem. Soc., Vol. 136, No. 2, 1989,pp. 590-591).

Systems doped with aluminum, scandium, yttrium and lanthanum inparticular were examined. It was found that in particular doping withaluminum delivers good results because, depending on the degree ofdoping, aluminum brings about the highest lithium ion conductivitycompared with other doping metals and, because of its cation radius(smaller than Ti⁴⁺) in the crystal, it can well take the spaces occupiedby the titanium.

Kosova et al. in Chemistry for Sustainable Development 13 (2005) 253-260propose suitable doped lithium titanium phosphates as cathodes, anodesand electrolytes for rechargeable lithium ion batteries.

Li_(1.3)Al_(0.3)Ti_(1.7)(PO₄) was proposed in EP 1 570 113 B1 as ceramicfiller in an “active” separator film which has additional lithium ionconductivity for electrochemical components.

Likewise, further doped lithium titanium phosphates, in particular dopedwith iron, aluminum and rare earths, were described in U.S. Pat. No.4,985,317.

However, very expensive production by means of solid-state synthesisstarting from solid phosphates, in which the obtained lithium titaniumphosphate is normally contaminated by further foreign phases such as forexample AlPO₄ or TiP₂O₇, is common to all of the above-named lithiumtitanium phosphates. Phase-pure lithium titanium phosphate or phase-puredoped lithium titanium phosphate has been unknown thus far.

The object of the present invention was therefore to provide phase-purelithium aluminum titanium phosphate, because this combines thecharacteristics of a high lithium ion conductivity with a low electricalconductivity. In particular, phase-pure lithium aluminum titaniumphosphate should have an even better ionic conductivity compared withlithium aluminum titanium phosphate of the state of the art because ofthe absence of foreign phases.

This object is achieved by the provision of phase-pure lithium aluminumtitanium phosphate of the formula Li_(1+x),Ti_(2−x)Al_(x)(PO₄)₃, whereinx is ≦0.4 and the level of magnetic metals and metal compounds of theelements Fe, Cr and Ni therein is 1 ppm.

Here, by the term “phase-pure” is meant that reflexes of foreign phasescannot be recognized in the X-ray powder diffractogram (XRD). Theabsence of foreign-phase reflexes in the lithium aluminum titaniumphosphate according to the invention, as is shown by way of example inFIG. 2 below, corresponds to a maximum proportion of foreign phases,such as e.g. AlPO₄ and TiP₂O₇, of 1%.

Foreign phases reduce the intrinsic ion conductivity, with the resultthat, compared with those of the state of the art, all of which containforeign phases, the phase-pure lithium aluminum titanium phosphatesaccording to the invention have a higher intrinsic conductivity than thelithium aluminum titanium phosphates of the state of the art.

Surprisingly, it was also found that the total level of magnetic metalsand metal compounds of Fe, Cr and Ni (ΣFe+Cr+Ni) in the lithium aluminumtitanium phosphate according to the invention is ≦1 ppm. In the case oflithium aluminum phosphates of the state of the art (obtained accordingto JP A 1990-2-225310) this value is normally between 2 and 3 ppm. Whenaccount is also taken of any disruptive zinc, the total content ΣFe+Cr+Ni+Zn=1.1 ppm in the lithium aluminum titanium phosphate accordingto the invention, compared with 2.3-3.3 ppm of a lithium aluminumtitanium phosphate according to the above-named state of the art.

In particular, the lithium aluminum titanium phosphate according to theinvention displays only an extremely small contamination by metallic ormagnetic iron and magnetic iron compounds (such as e.g. Fe₃O₄) of <0.5ppm. The determination of the concentrations of magnetic metals or metalcompounds is described in detail below in the experimental section.Customary values for magnetic iron or magnetic iron compounds in thelithium aluminum titanium phosphates previously known from the state ofthe art are approx. 1-1000 ppm. The result of contamination by metalliciron or magnetic iron compounds is that in addition to the formation ofdendrites associated with a drop in current the danger of short circuitswithin an electrochemical cell in which lithium aluminum titaniumphosphate is used as solid electrolyte increases significantly and thusrepresents a risk for the production of such cells on an industrialscale. This disadvantage can be avoided with the phase-pure lithiumaluminum titanium phosphate here.

Surprisingly, the phase-pure lithium aluminum titanium phosphateaccording to the invention also has a relatively high BET surface areaof <4.5 m²/g. Typical values are for example 2.0 to 3.5 m²/g. Lithiumaluminum titanium phosphates known from the literature on the other handhave BET surface areas of less than 1.5 m²/g.

The lithium aluminum titanium phosphate according to the inventionpreferably has a particle-size distribution of d₉₀<6 μm, d₅₀<2.1 μm andd₁₀<1 μm, which results in the majority of the particles beingparticularly small and thus a particularly high ion conductivity beingachieved. This confirms similar findings from the above-mentionedJapanese unexamined patent application, where it was also attempted toobtain smaller particle sizes by means of various grinding processes.Because of the extreme hardness of the lithium aluminum titaniumphosphate (Mohs' hardness>7, i.e. close to diamond), this is difficultto obtain with customary grinding processes, however.

In further preferred embodiments of the present invention, the lithiumaluminum titanium phosphate has the following empirical formulae:Li_(1.2)Ti_(1.8)Al_(0.2)(PO₄)_(3,) which has a very good total ionconductivity of approx. 5×10⁻⁴ S/cm at 293 K and—in the particularlyphase-pure form—Li_(1.3)Ti_(1.7)Al_(0.3)(PO₄)_(3,) which has aparticularly high total ion conductivity of 7×10⁻⁴ S/cm at 293 K.

The object of the present invention was furthermore to provide a methodfor producing the phase-pure lithium aluminum titanium phosphateaccording to the invention. This object is achieved by a method whichcomprises the following steps:

a) providing a concentrated phosphoric acid,

b) adding a mixture of a lithium compound, titanium dioxide and anoxygen-containing aluminum compound,

c) heating the mixture in order to obtain a solid intermediate product,

d) calcining the solid intermediate product.

Surprisingly it was found that, unlike all previously known syntheses ofthe state of the art, a liquid phosphoric acid can also be used insteadof solid phosphoric acid salts. The method according to the inventionthus proceeds as a defined precipitation of an aqueous precursorsuspension. The use of a phosphoric acid makes possible a simplerexecution of the method and thus also the option of removing impuritiesalready in solution or suspension and thus also obtaining products withgreater phase purity.

A concentrated phosphoric acid, i.e. for example 85% orthophosphoricacid, is preferably used as phosphoric acid, although in less preferredfurther embodiments of the present invention other concentratedphosphoric acids can also be used, such as for example metaphosphoricacid etc. All condensation products of orthophosphoric acid can also beused according to the invention such as: catenary polyphosphoric acids(diphosphoric acid, triphosphoric acid, oligophosphoric acids, etc.)annular metaphosphoric acids (tri-, tetrametaphosphoric acid) up to theanhydride of phosphoric acid P₂O₅ (in water).

According to the invention any suitable lithium compound can be used aslithium compound, such as Li₂CO₃, LiOH, Li₂O, LiNO₃, wherein lithiumcarbonate is particularly preferred because it is the mostcost-favourable source of raw material.

Practically any oxide or hydroxide or mixed oxide/hydroxide of aluminumcan be used as oxygen-containing aluminum compound. Aluminum oxide Al₂O₃is preferably used in the state of the art because of its readyavailability. In the present case it was found, however, that the bestresults are achieved with Al(OH)₃. Al(OH)₃ is even more cost-favourablecompared with Al₂O₃ and also more reactive than Al₂O₃, in particular inthe calcining step. Of course, Al₂O₃ can also be used in the methodaccording to the invention, albeit less preferably; however, thecalcining in particular then lasts longer compared with using Al(OH)₃.

The step of heating the mixture is carried out at a temperature of from200 to 300° C., preferably 200 to 260° C. and quite particularlypreferably of from 200 to 240° C. A gentle reaction which moreover canstill be controlled is thereby guaranteed.

The calcining takes place preferably at temperatures of from 830-1000°C., quite particularly preferably at 880-900° C., as below 830° C. thedanger of the occurrence of foreign phases is particularly great.

Typically, the vapour pressure of the lithium in the compoundLi_(1+x)Ti_(2−x)Al_(x)(PO₄)₃ increases at temperatures >950° C., i.e. attemperatures >950° C. the formed compounds Li_(1+x)Ti_(2−x)Al_(x)(PO₄)₃lose more and more lithium which settles as Li₂O and Li₂CO₃ on the ovenwalls in an air atmosphere. This can be compensated for e.g. by thelithium excess described below, but the precise setting of thestoichiometry becomes more difficult. Therefore, lower temperatures arepreferred and surprisingly also possible by the previous execution ofthe method compared with the state of the art. This result can beattributed to the use of aqueous concentrated phosphoric acid comparedwith solid phosphates of the state of the art.

Moreover, temperatures >1000° C. make greater demands of the oven andcrucible material.

The calcining is carried out over a period of from 5 to 10 hours. Infurther even more preferred embodiments of the present invention, asecond calcining step is carried out at the same temperature andpreferably for the same period, whereby a particularly phase-pureproduct is obtained.

In other preferred developments of the present invention, astoichiometric excess of the lithium compound is used in step b).Lithium compounds are, as already said above, often volatile at thereaction temperatures used, with the result that, depending on thelithium compound, work must here often be carried out with an excess.Here, preferably a stoichiometric excess of approx. 8% is then usedwhich represents a reduction in quantity of expensive lithium compoundof approx. 50% compared with the solid-state methods of the state of theart. Moreover, because the method is carried out via an aqueousprecipitation process, monitoring of the stoichiometry is madeparticularly easy compared with a solid-state method.

The subject of the present invention is also a phase-pure lithiumaluminum titanium phosphate of the formula Li_(1+x),Ti_(2−x)Al_(x)(PO₄)₃wherein x is 0.4, which can be obtained by the method according to theinvention and can be obtained particularly phase-pure within the meaningof the above definition by the execution of the method, and containssmall quantities of ≦1 ppm of magnetic impurities, as already describedabove. Also, all previously known products obtainable by solid-statesynthesis methods—as already said above—had further foreign phases inaddition to increased quantities of disruptive magnetic compounds,something which can be avoided here by executing the method according tothe invention in particular by using an (aqueous) concentratedphosphoric acid instead of solid phosphates.

The subject of the invention is also the use of the phase-pure lithiumaluminum titanium phosphate according to the invention as solidelectrolyte in a secondary lithium ion battery.

The object of the invention is further achieved by providing an improvedsecondary lithium ion battery which contains the phase-pure lithiumaluminum titanium phosphate according to the invention, in particular assolid electrolyte. Because of its high lithium ion conductivity, thesolid electrolyte is particularly suitable and particularly stable andalso resistant to short circuits because of its phase purity and lowiron content.

In preferred developments of the present invention, the cathode of thesecondary lithium ion battery according to the invention contains adoped or non-doped lithium transition metal phosphate as cathode,wherein the transition metal of the lithium transition metal phosphateis selected from Fe, Co, Ni, Mn, Cr and Cu. Doped or non-doped lithiumiron phosphate LiFePO₄ is particularly preferred.

In yet further preferred developments of the present invention, thecathode material additionally contains a doped or non-doped mixedlithium transition metal oxo compound different from the lithiumtransition metal phosphate used. Lithium transition metal oxo compoundssuitable according to the invention are e.g. LiMn₂O₄, LiCoO₂, NCA(LiNi_(1−x−y)Co_(x)Al_(y)O₂, e.g. LiNi_(0.8)Co_(0.15)Al_(0.05)O₂) or NCM(LiNi_(1/3)Co_(1/3)Mn_(1/3)O₂) . The proportion of lithium transitionmetal phosphate in such a combination lies in the range of from 1 to 60wt. %. Preferred proportions are e.g. 6-25 wt. %, preferably 8-12 wt. %in an LiCoO₂/LiFePO₄ mixture and 25-60 wt. % in an LiNiO₂/LiFePO₄mixture.

In yet further preferred developments of the present invention, theanode material of the secondary lithium ion battery according to theinvention contains a doped or non-doped lithium titanate. In lesspreferred developments the anode material contains exclusively carbon,for example graphite etc. The lithium titanate in the preferreddevelopment mentioned above is typically doped or non-doped Li₄Ti₅O₁₂,with the result that for example a potential of 2 volts vis-a-vis thepreferred cathode of doped or non-doped lithium transition metalphosphate can be achieved.

As already stated above, both the lithium transition metal phosphates ofthe cathode material as well as the lithium titanates of the anodematerial of the preferred development are either doped or non-doped.Doping takes place with at least one further metal or also with several,which leads in particular to an increased stability and cycle stabilityof the doped materials when used as cathode or anode. Metal ions such asAl, B, Mg, Ga, Fe, Co, Sc, Y, Mn, Ni, Cr, V, Sb, Bi, Nb or several ofthese ions, which can be incorporated in the lattice structure of thecathode or anode material, are preferred as doping material. Mg, Nb andAl are quite particularly preferred. The lithium titanates are normallypreferably rutile-free and thus equally phase-pure.

The doping metal cations are present in the above-named lithiumtransition metal phosphates or lithium titanates in a quantity of from0.05 to 3 wt. %, preferably 1 to 3 wt. % relative to the total mixedlithium transition metal phosphate or lithium titanate. Relative to thetransition metal (values in at %) or in the case of lithium titanates,relative to lithium and/or titanium, the quantity of doping metalcation(s) is 20 at %, preferably 5-10 at %.

The doping metal cations occupy either the lattice positions of themetal or of the lithium. Exceptions to this are mixed Fe, Co, Mn, Ni,Cr, Cu, lithium transition metal phosphates which contain at least twoof the above-named elements, in which larger quantities of doping metalcations may also be present, in the extreme case up to 50 wt. %.

Typical further constituents of an electrode of the secondary lithiumion battery according to the invention are, in addition to the activematerial, i.e. the lithium transition metal phosphate or the lithiumtitanate, carbon blacks as well as a binder.

Binders known per se to a person skilled in the art may be used here asbinder, such as for example polytetrafluoroethylene (PTFE),polyvinylidene difluoride (PVDF), polyvinylidene difluoridehexafluoropropylene copolymers (PVDF-HFP), ethylene-propylene-dieneterpolymers (EPDM), tetrafluoroethylene hexafluoropropylene copolymers,polyethylene oxides (PEO), polyacrylonitriles (PAN), polyacrylmethacrylates (PMMA), carboxymethylcelluloses (CMC), and derivatives andmixtures thereof.

Within the framework of the present invention, typical proportions ofthe individual constituents of the electrode material are preferably 80to 98 parts by weight active material electrode material, 10 to 1 partsby weight conductive carbon and 10 to 1 parts by weight binder.

Within the framework of the present invention, preferred cathode/solidelectrolyte/anode combinations are for exampleLiFePO₄/Li_(1.3)Ti_(1.7)Al_(0.3)(PO₄)₃/Li_(x)Ti_(y)O with a single-cellvoltage of approx. 2 volts which is well suited as substitute forlead-acid cells orLiCo_(z)Mn_(y)Fe_(x)PO₄/Li_(1.3)Ti_(1.7)Al_(0.3)(PO₄)₃/Li_(x)Ti_(y)O,wherein x, y and z are as defined further above, with increased cellvoltage and improved energy density.

The invention is explained in more detail below with the help ofdrawings and examples which are not to be understood as limiting thescope of the present invention. There are shown in:

FIG. 1 the structure of the phase-pure lithium aluminum titaniumphosphate according to the invention,

FIG. 2 an X-ray powder diffractogram (XRD) of a lithium aluminumtitanium phosphate according to the invention,

FIG. 3 an X-ray powder diffractogram (XRD) of a conventionally producedlithium aluminum titanium phosphate,

FIG. 4 the particle-size distribution of the lithium aluminum titaniumphosphate according to the invention.

1. Measurement Methods

The BET surface area was determined according to DIN 66131 (DIN-ISO9277).

The particle-size distribution was determined according to DIN 66133 bymeans of laser granulometry with a Malvern Mastersizer 2000.

The X-ray powder diffractogram (XRD) was measured with an X'Pert PROdiffractometer, PANalytical: Goniometer Theta/Theta, Cu anode PW 3376(max. output 2.2 kW), detector X'Celerator, X'Pert Software.

The level of magnetic constituents in the lithium aluminum titaniumphosphate according to the invention is determined by separation bymeans of magnets followed by decomposition by acid and subsequent ICPanalysis of the formed solution.

The lithium aluminum titanium phosphate powder to be examined issuspended in ethanol with a magnet of a specific size (diameter 1.7 cm,length 5.5 cm<6000 Gauss). The ethanolic suspension is exposed to themagnet in an ultrasound bath with a frequency of 135 kHz for 30 minutes.The magnet attracts the magnetic particles from the suspension or thepowder. The magnet with the magnetic particles is then removed from thesuspension. The magnetic impurities are dissolved with the help ofdecomposition by acid and this is examined by means of ICP (ionchromatography) analysis, in order to determine the precise quantity aswell as the composition of the magnetic impurities. The apparatus forICP analysis was an ICP-EOS, Varian Vista Pro 720-ES.

Example 1

Production of Li_(1.3)Al_(0.3)Ti_(1.7)(PO₄)₃

1037.7 g orthophosphoric acid (85%) was introduced into a reactionvessel. A mixture of 144.3 g Li₂CO₃, 431.5 g TiO₂ (in anatase form) and46.8 g Al(OH₃) (Gibbsite) was added slowly via a fluid channelaccompanied by vigorous stirring with a Teflon-coated anchor stirrer. Asthe Li₂CO₃ with the phosphoric acid reacted off accompanied by strongfoaming of the suspension because of the formation of CO₂, the admixturewas added very slowly over a period of from 1 to 1.5 hours. Towards theend of the addition, the white suspension became more viscous butremained capable of forming drops.

The mixture was then heated to 225° C. in an oven and left at thistemperature for two hours. A hard, friable crude product, only partlyremovable from the reaction vessel with difficulty, forms. The completesolidification of the suspension from liquid state via a rubberyconsistency took place relatively quickly. However, e.g. a sand or oilbath can also be used instead of an oven.

The crude product was then finely ground over a period of 6 hours inorder to obtain a particle size of <50 μm.

The finely ground premixture was heated from 200 to 900° C. within sixhours at a heat-up rate of 2° C. per minute, as otherwise crystallineforeign phases were detectable in the X-ray powder diffractogram (XRD).The product was then sintered at 900° C. for 24 hours and then finelyground in a ball mill with porcelain spheres. The total quantity ofmagnetic Fe, Cr and Ni or their magnetic compounds was 0.75 ppm. Thetotal quantity of Fe and its magnetic compounds was 0.25 ppm.

Example 2

Li_(1.3)Al_(0.3)Ti_(1.7)(PO₄)₃ was synthesized as in Example 1, butafter the end of the addition of the mixture of lithium carbonate, TiO₂and Al(OH)₃, the white suspension was transferred into a vessel withanti-adhesion coating, for example into a vessel with Teflon walls. Theremoval of the cured intermediate product was thereby greatly simplifiedcompared with Example 1. The analysis data corresponded to those ofExample 1.

Example 3

Li_(1.3)Al_(0.3)Ti_(1.7)(PO₄)₃ was synthesized as in Example 2, exceptthat the ground intermediate product was also pressed into pelletsbefore the sintering. The analysis data corresponded to those of Example1.

Example 4

Li_(1.3)Al_(0.3)Ti_(1.7)(PO₄)₃ was synthesized as in Example 2 or 3,except that both with the pellets and with the finely groundintermediate product, a first calcining was carried out over 12 hoursafter cooling to room temperature followed by a second calcining over afurther 12 hours at 900° C. In the case of the latter, no signs offoreign phases were found in the product. The total quantity of magneticFe, Cr and Ni or their magnetic compounds was 0.76 ppm. The quantity ofFe and its magnetic compound was 0.24 ppm. A comparison example producedaccording to JP A 1990 2-225310 showed, on the other hand, a quantity Σof Fe, Cr, Ni of 2.79 ppm and of magnetic iron or iron compounds of 1.52ppm.

The structure of the product Li_(1.3)Al_(0.3)Ti_(1.7)(PO₄)₃ obtainedaccording to the invention is shown in FIG. 1 and is similar to aso-called NASiCON (Na⁺ superionic conductor) structure (see Nuspl et al.J. Appl. Phys. Vol. 06, No. 10, p. 5484 et seq. (1999)).

The three-dimensional Li⁺ channels of the crystal structure and asimultaneously very low activation energy of 0.30 eV for the Limigration in these channels bring about a high intrinsic Li ionconductivity. The Al doping scarcely influences this intrinsic Li⁺conductivity, but reduces the Li ion conductivity at the particleboundaries.

In addition to Li_(3x)La_(2/3−x)TiO₃ compounds,Li_(1.3)Al_(0.3)Ti_(1.7)(PO₄)₃ is the solid-state electrolyte with thehighest Li⁺ ion conductivity known in literature.

As can be seen from the X-ray powder diffractogram (XRD) of the productfrom Example 4 in FIG. 2, particularly phase-pure products result fromthe reaction process according to the invention.

FIG. 3 shows, in comparison to this, an X-ray powder diffractogram of alithium aluminum titanium phosphate of the state of the art producedaccording to JP A 1990 2-225310 with foreign phases such as TiP₂O₇ andAlPO₄. The same foreign phases are also found in the material describedby Kosova et al. (see above).

The particle-size distribution of the product from Example 4 is shown inFIG. 4 which has a purely monomodal particle-size distribution withvalues for d₉₀ of <6 μm, d₅₀ of <2.1 μm and d₁₀<1 μm.

1. Phase-pure lithium aluminum titanium phosphate of the formulaLi_(1+x)Ti_(2−x)Al_(x)(PO₄)_(3,) wherein x is ≦0.4 and the level ofmagnetic metals and magnetic metal compounds of the elements Fe, Cr andNi therein is ≦1 ppm.
 2. Lithium aluminum titanium phosphate accordingto claim 1, the particle-size distribution d₉₀ of which is <6 μm. 3.Lithium aluminum titanium phosphate according to claim 1 or 2, the metaliron and magnetic iron compounds content of which is <0.5 ppm. 4.Lithium aluminum titanium phosphate according to claim 3, wherein thevalue for x is 0.2 or 0.3.
 5. Method for producingLi_(1+x)Ti_(2−x)Al_(x)(PO₄)₃, wherein x is ≦0.4, according to one of theprevious claims, comprising the steps of a) providing a concentratedphosphoric acid b) adding a mixture of a lithium compound, titaniumdioxide and an oxygen-containing aluminum compound, c) heating themixture in order to obtain a solid intermediate product, d) calciningthe solid intermediate product.
 6. Method according to claim 5, whereinliquid concentrated phosphoric acid or aqueous concentrated phosphoricacid is used as phosphoric acid; and/or wherein concentratedorthophosphoric acid or 85% orthophosphoric acid is used as phosphoricacid.
 7. Method according to claim 5 or 6, wherein lithium carbonate isused as lithium compound.
 8. Method according to one of claims 5 to 7,wherein Al(OH)₃ is used as oxygen-containing aluminum compound. 9.Method according to one of claims 5 to 8, wherein the step of heating iscarried out at a temperature of from 200 to 300° C.
 10. Method accordingto claim 9, wherein the calcining takes place at 850 to 1000° C. 11.Method according to claim 10, wherein the calcining is carried out overa period of from 5 to 24 hours.
 12. Method according to one of theprevious claims 5 to 11, wherein a stoichiometric excess of lithiumcompound is used in step b).
 13. Phase-pure lithium aluminum titaniumphosphate of the formula Li_(1+x)Ti_(2−x)Al_(x)(PO₄)₃, wherein x is≦0.4, obtainable by the method according to one of the previous claims 5to
 12. 14. Use of phase-pure lithium aluminum titanium phosphateaccording to claim 1 to 4 or 13 as solid electrolyte in a secondarylithium ion battery.
 15. Secondary lithium ion battery containingphase-pure lithium aluminum titanium phosphate according to one of claim1 to 4 or
 13. 16. Secondary lithium ion battery according to claim 15,further containing, as cathode material, a doped or non-doped lithiumtransition metal phosphate.
 17. Secondary lithium ion battery accordingto claim 16, wherein the transition metal of the lithium transitionmetal phosphate is selected from Fe, Co, Ni, Mn, Cu, Cr.
 18. Secondarylithium ion battery according to claim 17, wherein the transition metalis Fe.
 19. Secondary lithium ion battery according to claim 18, whereinthe cathode material contains a further doped or non-doped lithiumtransition metal oxo compound.
 20. Secondary lithium ion batteryaccording to one of claims 15 to 19, wherein the anode material containsa doped or non-doped lithium titanate.